EP2403713A1 - Laminated polymer film and solar module made thereof - Google Patents

Laminated polymer film and solar module made thereof

Info

Publication number
EP2403713A1
EP2403713A1 EP09789931A EP09789931A EP2403713A1 EP 2403713 A1 EP2403713 A1 EP 2403713A1 EP 09789931 A EP09789931 A EP 09789931A EP 09789931 A EP09789931 A EP 09789931A EP 2403713 A1 EP2403713 A1 EP 2403713A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
laminated film
layer
film
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09789931A
Other languages
German (de)
French (fr)
Inventor
Ruofei ZHAO
Qiuju Wu
Shijie Ren
Bo Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2403713A1 publication Critical patent/EP2403713A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S977/814—Group IV based elements and compounds, e.g. CxSiyGez, porous silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the present invention relates to a laminated polymer film with improved bonding strength between individual film layers.
  • the laminated polymer film not only has improved bonding strength between individual film layers, but also has improved bonding strength with an ethylene-vinyl acetate copolymer that serves as an encapsulant for solar cell components.
  • the present invention also relates to a solar module made of such a laminated polymer film.
  • Solar energy is a clean, pollution-free and inexhaustible energy source. At present, solar energy is utilized primarily via its conversion into electricity by solar modules. The electricity is then used to power electric water heaters, electric vehicles, and satellite components.
  • a solar module refers to a photovoltaic device generating electricity directly from light, particularly, from sunlight.
  • solar modules include modules that accommodate crystalline silicon solar cells such as monocrystalline silicon solarcells, polycrystalline silicon solar cells, and nano-silicon solar cells, and thin-film solar cells such as non-crystalline thin-film silicon solar cells, cadmium telluride thin-film solar cells, and copper indium gallium selenide thin-film solar cells.
  • a crystalline silicon solar module mainly comprises a back sheet, an encapsulant, a photovoltaic circuit and a front sheet.
  • the structure of a thin- film solar cell mainly comprises a photovoltaic circuit placed on a substrate (for example, a glass sheet, polymer sheet or stainless steel sheet), an encapsulant placed on the other surface of the photovoltaic circuit and the substrate, and a front sheet or back sheet placed on the encapsulant.
  • the encapsulant is used in solar modules to bond the front sheet, the photovoltaic circuit and/or the back sheet together.
  • a lamination operation carried out at about 150 0 C a molten encapsulant flows into voids in a solar cell to encapsulate the solar cell.
  • encapsulation materials include ethylene -vinyl acetate copolymers and ionic polymers.
  • ionic polymers have disadvantages, including high prices, difficulties in processing and very high hardness.
  • ethylene-vinyl acetate copolymers (EVA) have advantages of ease of processing, moderate prices and appropriate flexibility. Therefore, they are the most commonly used polymeric encapsulation materials at present.
  • the primary role of the front sheet in a solar module is to protect solar cells against mechanical impact and weathering.
  • the front sheet In order to make full use of the incident light, the front sheet must have a high light transmittance in a certain range of the spectrum (e.g., from 400 to 1,100 nm for crystalline silicon solar cells).
  • the front sheet of prior art solar modules is mainly formed of glass (usually low-iron, tempered flint glass with a thickness of 3 to 4 mm) or polymeric materials.
  • the primary role of the back sheet in a solar module is to protect the solar cells and the encapsulant against moisture and oxidation.
  • the back sheet is also used as a mechanical shield to prevent scratches and serves as an insulator. Therefore, the back sheet is required to have excellent moisture barrier properties and flexibility, and a good bonding strength with the encapsulant to prevent oxygen and moisture from penetrating into the solar module.
  • a common back sheet of a solar module is a multi-layer laminated film, mainly comprising a substrate (e.g., a polyester substrate) and a bonding layer on one surface of the substrate.
  • the bonding strength between the substrate (e.g., a polyester substrate) and the bonding layer is not completely satisfactory.
  • a laminated film that has excellent moisture and oxygen barrier properties, excellent bonding strength between its film layers, and excellent bonding strength with an ethylene-vinyl acetate copolymer that serves as an encapsulant. Also provided is a crystalline silicon solar module that utilizes the laminated film of the present invention for its back sheet.
  • a thin-film solar module that utilizes the laminated film of the present invention for its back sheet or front sheet.
  • a laminated film which comprises: (a) a polyester substrate having a first surface and a second surface comprising polymers selected from the group consisting of polyC 2 - 6 alkylene phthalates, PoIyC 2 -O alkylene naphthalates, and mixtures or blends thereof;
  • a bonding layer on the primer layer comprises a copolymer of ethylene and one or more monomers selected from the group consisting of Ci_4 alkyl acrylates, Ci_4 alkyl methacrylates, methacrylic acid, glycidyl methacrylate, and maleic anhydride; and (e) a protective layer on the adhesive layer comprising a fluoropolymer with a tensile modulus of greater than 150 Kpsi.
  • a solar module which comprises a front sheet, a back sheet and a photovoltaic circuit that is encapsulated with an ethylene-vinyl acetate copolymer material, wherein the back sheet is made of the laminated film of the present invention.
  • a solar module which comprises a photovoltaic circuit placed on a glass sheet, polymer sheet or stainless steel sheet, and a front sheet and/or a back sheet made of the laminated film of the present invention.
  • the laminated film of the present invention includes a substrate, wherein the substrate material is selected from polyesters or fluorine-containing polymers.
  • a laminated film may comprise a single layer or multiple layers of polyester and a single layer or multiple layers of fluorine-containing polymer, for example, a laminated film of two layers or multiple layers of polyester and fluorine- containing polymer.
  • the substrate may be selected from:
  • polyesters for example, polyC2-6 alkylene phthalates, polyC2-6 alkylene naphthalates, or binary copolymers, polybasic polymers or mixtures thereof;
  • fluorine-containing polymers for example, polyC2-6 alkylene phthalates, polyC2-6 alkylene naphthalates, or binary copolymers, polybasic polymers or mixtures thereof;
  • polyesters or fluorine-containing polymers with a coat of metal or metal oxide/non-metal oxide on the surface;
  • polyesters When polyesters are used for making substrates, there are no specific restrictions to the polyesters. It may be any polyester film known in the art. It may also be a laminated double-layer or multi-layer polyester film. In one embodiment, the total thickness of the polyester substrate is 30-350 microns, preferably 50-300 microns, and more preferably 70-250 microns.
  • polyester material suitable for the substrate include, for example, polyC2-6 alkylene phthalates, preferably polyC2-4 alkylene phthalates, such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene o-phthalate, polytrimethylene o-phthalate, polybutylene o-phthalate, and polyhexylene o-phthalate, preferably polyethylene terephthalate; polyC2-6 alkylene naphthalates, preferably PoIyC 2-4 alkylene naphthalates, such as polyethylene naphthalate, polytrimethylene naphthalate, and polybutylene naphthalate; and copolymers and blends of two or more above materials.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • polybutylene terephthalate polyhexylene terephthalate
  • Suitable polyester substrate may be formed by film-casting and then treating by biaxial orientation to further improve mechanical strength and gas barrier properties.
  • the film has good mechanical, dielectric, and gas barrier properties.
  • Suitable polyester substrates may also be purchased from the market, for example, polyethylene terephthalate sheets of various thicknesses may be purchased from E. I. du Pont de Nemours and Company, Wilmington, DE, USA ("DuPont").
  • fluorine-containing polymers suitable for making the substrate may be a polymer film formed by any fluorine-containing polymer known in the art.
  • suitable fluorine-containing polymers include polymers of fluoroethylene; copolymers of fluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of vinylidene fluoride; copolymers of vinylidene fluoride with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of chlorotrifluoroethylene; copolymers of chlorotrifluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of tetrafluoroethylene; and copolymers of tetrafluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers.
  • Non-restrictive examples of the other non-fluorinated, partially-fluorinated or perfluorinated monomers include, for example, ethylene, propylene, fluoroethylene, ethylene fluoride, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, tetrafluoroethylene, perfluoroalkoxyvinyl ether, perfluoropropylene and the like.
  • Suitable fluorine-containing polymers for the substrate may also be purchased from the market, for example, it may be a TedlarTM polyfluoroethylene purchased from DuPont, or polyvinylidene fluorides, ethylene -tetrafluoroethylene copolymers or tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymers purchased from Dyneon LLC (Oakdale, Minn.).
  • the fluorine-containing polymer substrate may also be a laminated film of double-layer or multi-layer fluorine-containing polymer.
  • the substrate is a laminated film formed from a layer of polyfluoroethylene and a layer of polyvinylidene fluoride, ethylene -tetrafluoroethylene copolymer or tetrafluoroethylene-hexafluoropropylene/vinylidene fluoride copolymer.
  • the total thickness of the fluorine-containing polymer substrate is 20-350 microns, preferably 20-300 microns, and more preferably 20-250 microns.
  • polyester substrate or fluorine-containing polymer substrate On one or two major surfaces of the above-described polyester substrate or fluorine-containing polymer substrate is coated a single layer or multiple layers of a surface coat selected from metal, metal oxide and non-metal oxide.
  • the surface coated substrate forms a polyester metal-coated substrate or a fluorine-containing metal-coated polymer substrate.
  • the suitable metal oxide or non-metal oxide may be any metal oxide or non-metal oxide commonly used in the art.
  • Such an oxide layer is usually deposited by using a chemical vapor deposition (CVD) method on the surface of the polyester or fluorine-containing polymer.
  • the thickness of the oxide layer is usually 50 to 4000 A, preferably 100 to 1000 A.
  • the suitable metal coat It may be any metal coat commonly used in the art, for example, a silver foil, an aluminum foil, or a tin foil.
  • An aluminum foil is usually used when cost and other factors are in consideration.
  • the thickness of the metal coat It may be any thickness conventionally used in the art. In one embodiment, a metal coat is used with a thickness of 5-50 microns, preferably 7-25 microns.
  • a metal coat (e.g., aluminum foil) may be laminated on the polyester or fluorinated polymer substrate by using any methods known in the art.
  • an adhesive may be used to facilitate the lamination process.
  • the total thickness of the polyester substrate or fluorine-containing polymer substrate that has a metal or metal oxide/non-metal oxide coat on the surface is 8-350 microns, preferably 10-300 microns, and more preferably 12-250 microns.
  • the laminated substrate of the present invention may also be a laminated film made of a polyester and a fluorine-containing polymer. It may be a laminated film made from a single layer or multiple layers of polyester and a single layer or multiple layers of fluorine-containing polymer.
  • the polyester is the same polyester material as what was described with the polyester substrate above. It may be a laminate made from a single layer of polyester material or multiple layers of polyester material. In one embodiment, on one or two major surfaces of the polyester layer, a layer of the above described fluorine-containing polymer is laminated.
  • the laminate of polyester- fluorine-containing polymer is formed by alternate polyester layers and fluorine-containing polymer layers.
  • the polyester layer is a laminate made from a single layer of polyester, or two layers, or multiple layers of polyester.
  • the laminate of fluorine-containing polymer may be a single layer of fluorine-containing polymer, or two layers, or multiple layers of fluorine-containing polymer.
  • the thickness may be any known thickness conventionally used in the art.
  • a fluorine-containing polymer layer is used with a thickness of 15-
  • the total thickness of the laminated film substrate of polyester- fluorine- containing polymer is 30-350 microns, preferably 50-300 microns, and more preferably 70-250 microns.
  • the method of laminating the polyester layer with the fluorine-containing polymer layer may be any conventional method known in the art.
  • an adhesive is used for bonding the fluorine-containing polymer layer to the polyester substrate.
  • the adhesives for bonding the fluorine-containing polymer layer to the polyester layer may be any conventional adhesives known in the art.
  • a polyurethane adhesive is used, which is formed by mixing PP5250 and 15200 adhesives manufactured by Mitsubishi of Japan according to a ratio of 8-10:1 by weight, preferably 9:1.
  • the thickness of the adhesive layer for bonding the fluorine-containing polymer to the polyester, as long as the adhesion strength can meet the requirements.
  • the thickness of the adhesive layer is in the range of 1-30 microns, preferably 5-25 microns, and more preferably 8-18 microns.
  • a laminated film of two layers or multiple layers of polyester/fluorine-containing polymer is used as a substrate.
  • the laminated film is selected from the group consisting of polyfluoroethylene/poly ethylene terephthalate laminated film, polyvinylidene fluoride/polyethylene terephthalate laminated film, polyfluoroethylene/polyethylene naphthalate laminated film, polyfluoroethylene/polyethylene terephthalate/polyfluoroethylene laminated film, and polyethylene terephthalate/polyethylene terephthalate/polyethylene terephthalate laminated film.
  • a single-layer or multi-layer laminated film comprising a layer of aluminum foil with a thickness of 3-50 microns is used as a substrate.
  • the substrate include, for example, polyfluoroethylene/aluminum foil/polyethylene terephthalate.
  • the aluminum foil may be bonded with an adhesive on the surface of fluorine-containing polymer or polyester.
  • a polyester film with a metal oxide coat on its surface is used as a substrate.
  • Non-restrictive examples of the substrate include, for example, polyfluoroethylene/aluminum oxide/polyethylene terephthalate/poly ethylene terephthalate .
  • the substrate may contain various types of additives, such as photo- stabilizers, thermal stabilizers, hydrolysis resistant agents, surface modifiers, fluorescent brightening agents, light reflecting agents, dyes, and pigments. Particular suitable additives are commonly used additives in the art.
  • the substrate is a laminated film (for example, polyester laminated film or laminated film of polyester- fluorine-containing polymer)
  • the additives may optionally be added into each layer of the laminated film.
  • the laminated film comprises a bonding layer on one major surface of the substrate for bonding the back sheet to the encapsulant of ethylene-vinyl acetate copolymer.
  • Suitable materials used for forming the bonding layer are ethylene copolymer materials, which are selected from the following groups: ethylene-Ci_ 4 alkyl methacrylate copolymers and ethylene-Ci_ 4 alkyl acrylate copolymers, for example, ethylene-methyl methacrylate copolymers, ethylene -methyl acrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-propyl methacrylate copolymers, ethylene -propyl acrylate copolymers, ethylene -butyl methacrylate copolymers, ethylene-butyl acrylate copolymers, and mixtures of two or more copolymers thereof, wherein copolymer units resulting from
  • the thickness of the bonding layer suitable for the laminated film is 10- 400 microns, preferably 40-200 microns.
  • the bonding layer may have an encapsulation layer for encapsulating the solar module (usually polyethylene-vinyl acetate, polyethylene-methyl acrylate, polyethylene-butyl acrylate, polyethylene -methacrylic acid, ion polymer, polyurethane, or polyvinyl butyral) and has good adhesion properties, good dielectric properties and aging resistance.
  • an encapsulation layer for encapsulating the solar module usually polyethylene-vinyl acetate, polyethylene-methyl acrylate, polyethylene-butyl acrylate, polyethylene -methacrylic acid, ion polymer, polyurethane, or polyvinyl butyral
  • the bonding layer may contain various types of additives. Suitable non- restrictive examples are photo-stabilizers, thermal stabilizers, slip agents, light reflecting additives, and pigments.
  • the bonding layer may be bonded to the substrate by using any methods known in the art.
  • suitable bonding methods include, for example, melting suitable copolymer resin in an extruder and then coating the melt on the substrate surface by extrusion through an extruder die, or adhering the bonding layer to the substrate with an adhesive.
  • the bonding layer is bonded to the substrate without the use an adhesive, particularly without the use an adhesive that is diluted with an organic solvent.
  • PET polyethylene terephthalate
  • the bonding layer may be a laminate of a single-layer material or a double-layer or multi-layer material, for example, the bonding layer of the present invention may be a 2-8 layer, preferably 2-6 layer, more preferably 2-3 layer laminate of the polymer material selected respectively from above-described ethylene copolymer materials.
  • the bonding layer is a tri-layer laminate, wherein one layer is a polymer sheet formed from polymer materials selected from ethylene- Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, and ethylene-maleic anhydride copolymers.
  • Another layer is a polymer sheet formed from a polybasic polymer of ethylene with at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride.
  • Another layer is a polymer sheet formed from a glycidyl methacrylate-containing polybasic polymer of ethylene and glycidyl methacrylate formed from at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid and maleic anhydride.
  • the tri-layer polymer sheet has approximately the same thickness so that the final polymer sheet that serves as a bonding layer has a thickness of 10-400 microns, preferably 40-200 microns.
  • the bonding layer is a double-layer laminate, wherein one layer is a polymer sheet formed from polymer materials selected from ethylene-Ci_ 4 alkyl methacrylate copolymers, ethylene-Ci_ 4 alkyl acrylate copolymers, ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene with at least two monomers selected from Ci_4 alkyl methacrylate, ethylene-Ci_ 4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride; and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate and at least one co-monomer selected from
  • Another layer is a polymer sheet formed from polymer materials selected from polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co- monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and blends of two or more polymers described above.
  • the bonding layer is a tri-layer laminate, wherein one layer is a polymer sheet formed from polymer materials selected from ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene -maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride; and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co-monomer selected from Ci_ 4 alkyl methacrylate, Ci_ 4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and blends of two or more polymers described above.
  • Another layer is a polymer sheet formed by polymer materials selected from polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_ 4 alkyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, or blends of two or more polymers described above.
  • Yet another layer is a polymer sheet formed from polymer materials selected from polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene- methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co- monomer selected from Ci_ 4 alkyl methacrylate, Ci_ 4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, or blends of two or more polymers described above.
  • the polyethylene and polypropylene suitable for the bonding layer include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, metallocene-derived low density polyethylene, and homopolypropylene.
  • Two or more extruders may be used for bonding the multi-layer laminated film of the bonding layer to the substrate of the present invention by extrusion- coating.
  • the substrate surface may be surface-treated.
  • suitable surface treatment methods may be any conventional methods known in the art.
  • it may be a corona treatment, flame treatment, or primer treatment.
  • suitable primers include, for example, imine primers and amine primers.
  • the primer thickness is usually less than 1.5 microns, suitably less than 1.2 microns, preferably less than 1 micron, more preferably less than 0.99 microns, most preferably less than 0.8 microns, and optimally less than 0.5 microns.
  • the primer thickness can be less than 0.45 microns, less than 0.4 microns, less than 0.3 microns or less than 0.25 microns.
  • the primer thickness is 0.01-0.99 microns, suitably 0.01-0.8 microns, preferably 0.01-0.5 microns.
  • the bonding layer is directly placed on the substrate.
  • the phrase "bonding layer is directly placed on the substrate” refers to a situation where there is no coat or layer applied between the bonding layer and the substrate for improving the bonding strength between the two.
  • the laminated film has high bonding or peeling strength between the substrate and the bonding layer. Compared with the bonding strength between the substrate and bonding layer found in the art, the bonding strength between the two layers of the laminated film is higher, and the bonding strength may be as high as about 10N/cm according to a T-type peeling test.
  • the laminated film is particularly suitable for making a back sheet of a crystalline silicon solar module or for making a front sheet or a back sheet of a thin film solar module.
  • This type of back sheet or front sheet not only has good peeling strength, but also avoids delamination between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer due to a very high bonding strength between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer, and can effectively extend the service life of solar modules.
  • the present invention is further exemplified by the following illustrative examples.
  • a laminated film was cut into sample strips of 2.54 cm in width and 10 cm in length, and the bonding layer and the substrate were fixed respectively in the upper and lower grips of an extension meter to carry out a peeling test at a speed of 5 in/min.
  • a laminated film (with the bonding layer adjacent to the encapsulation film), an encapsulation film of ethylene-vinyl acetate copolymer and a piece of glass were stacked in a proper order and placed in a laminating press for cross- linking for 15 min under an operation temperature of 140 0 C. Then, the sample was cut into strips of 2.54 cm in width and 10 cm in length.
  • the laminated film of the back sheet and the encapsulant/glass layer were fixed respectively in the upper and lower grips of an extension meter to carry out a peeling test at a speed of 5 in/min.
  • Hydrothermal aging test for solar cell components includes sorting the solar cells, single welding, serial welding, stacking, laminating, component testing, framing and cleaning.
  • the hydrothermal aging test of laminated solar cell components was carried out in a climatic chamber VC4018 (purchased from V ⁇ tsch Industrietechnik GmbH, Germany) according to Clause 10.13 of IEC 61215 Standard. Solar cell components for testing were maintained for 1,000 hrs under the hydrothermal conditions (85 0 C and 85% relative humidity). Then, the components were taken out, and the encapsulation layer of ethylene-vinyl acetate copolymer was peeled off.
  • the peeled encapsulation layer of ethylene-vinyl acetate copolymer was tested for its yellowing index, ⁇ YI, on a Lambda 950 UV/visible/Near-IR spectrophotometer (including a 150 mm integrating sphere) from Perkin Elmer, U.S.A.:
  • ⁇ YI Y 1 - Y 0
  • Yo is the value of extinction of the encapsulation layer of ethylene-vinyl acetate copolymer peeled without being treated under the hydrothermal conditions, measured with a Lambda 950 UV/visible/Near-IR spectrophotometer.
  • Y 1 is the value of extinction of the encapsulation layer of ethylene-vinyl acetate copolymer peeled after being treated under the hydrothermal conditions, which was also measured with a Lambda 950 UV/visible/Near-IR spectrophotometer. If the index equals zero, it means that the encapsulant was not influenced by outside oxygen and moisture when placed under the hydrothermal conditions. In other words, the solar cell has excellent air tightness. Therefore, the smaller the index, the better.
  • a laminated film was cut into sample strips of 2.54 cm in width and 10 cm in length, and the top layer and the bottom layer were fixed respectively in the upper and lower grips of an extension meter to carry out a peeling test at a speed of 5 in/min.
  • PVF/PET/PVF purchased from Isovolta Group was used. PVF is an abbreviation for 'polyvinylidene fluoride.'
  • the peeling strength between PVF and PET was determined to be 4 N/cm.
  • the peeling strength between the back sheet and the EVA encapsulation layer after lamination was determined to be
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the yellowing index ⁇ YI was determined to be 0.6.
  • the adhesive used was a 9: 1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan.
  • the adhesive layer was 12 microns thick.
  • Epomin P- 1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.90 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-methacrylate copolymer (with 80% being from ethylene monomer) was extrusion-coated at 290 0 C on the primed surface with a thickness of 75 microns to form a laminated film.
  • the peeling strength between the polyethylene terephthalate sheet and the ethylene-methacrylate copolymer layer was determined to be 21 N/cm. Compared with the peeling strength of the conventional laminated film discribed in Comparative Example 1 , the laminated film of the present invention is increased 4 fold.
  • the peeling strength was determined to be 12 N/cm.
  • the peeling strength between the ethylene-methacrylate copolymer layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 81 N/cm. Compared with the peeling strength between the conventional laminated film (Comparative Example 1) and the ethylene-vinyl acetate copolymer encapsulant, the peeling strength between the laminated film of this example and the ethylene-vinyl acetate copolymer encapsulant is increased by about 16 fold.
  • a 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the above-described laminated film from Example 1 has the above- described ethylene -methacrylate copolymer facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 177 watts.
  • PET as described in Example 1 of JP2008- 108947
  • ethylene- methacrylate copolymer as described in Example 1 of JP2008- 108947
  • a polyurethane adhesive polyyester-based polyurethane matrix and a mixed curing agent of isophorone diisocyanate (IPDI) and xylylene diisocyanate (XDI)
  • IPDI isophorone diisocyanate
  • XDI xylylene diisocyanate
  • the adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan.
  • the adhesive layer was 12 microns thick.
  • Epomin P-1050 made by Nippon Shokubai Co., Ltd.
  • Epomin P-1050 made by Nippon Shokubai Co., Ltd.
  • a layer of ethylene-methacrylate copolymer (with 80% w/w being from ethylene monomer) containing 5% (w/w) of titanium dioxide additive by total weight of the copolymer was extrusion-coated at 290 0 C on the primed surface to form a laminated film with a thickness of 75 microns.
  • the peeling strength between the polyethylene terephthalate sheet and the ethylene-methacrylate copolymer layer was determined to be 20 N/cm. After accelerated hydrothermal aging under conditions of 85 0 C and 85% RH for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
  • the peeling strength between the ethylene-methacrylate copolymer layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
  • a 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.;
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.
  • the output power of the assembled solar cells was determined to be 177 watts.
  • the adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan.
  • the adhesive layer is 12 microns thick.
  • Epomin P-1050 made by Nippon Shokubai Co., Ltd. was coated as a 0.45 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a 1 :9 (w/w) mixture of ethylene -maleic anhydride copolymer (with 80% w/w being from ethylene monomer) and ethylene-methacrylate copolymer (with 80% w/w being from ethylene monomer) containing 5% (w/w) of titanium dioxide additive by total weight of the copolymer mixture was extrusion-coated on the primed surface to form a laminated film with a thickness of 75 microns.
  • the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 23 N/cm. After accelerated hydrothermal aging under conditions of 85 0 C and 85% RH for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
  • the peeling strength between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer was determined to be 80 N/cm.
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the above-described laminated film from Example 3 has the above- described copolymer mixture facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 178 watts. Hydrothermal aging test on solar cell components
  • the adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan.
  • the adhesive layer was 12 microns thick.
  • Epomin P-1050 made by Nippon Shokubai Co., Ltd.
  • Epomin P-1050 made by Nippon Shokubai Co., Ltd.
  • a layer of ethylene-butyl acrylate-methacrylic acid terpolymer (the ratio of the three monomer units is 88.5: 7.5: 4 by weight) was extrusion-coated on the primed surface to form a laminated film with a thickness of 75 microns.
  • the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 25 N/cm. After accelerated hydrothermal aging under conditions of 85 0 C and 85% RH for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
  • the peeling strength between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer was determined to be 82 N/cm.
  • a 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.
  • the above-described laminated film from Example 4 has the above- described terpolymer facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 175 watts.
  • the adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from
  • the adhesive layer was 12 microns thick.
  • Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.48 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-butyl acrylate-glycidyl methacrylate terpolymer
  • the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 26
  • the peeling strength was determined to be 11 N/cm.
  • the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the above-described laminated film from Example 5 has the above- described terpolymer facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 178 watts.
  • the adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan.
  • the adhesive layer was 12 microns thick.
  • Epomin P- 1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.5 micron-thick primer on another major surface of the polyethylene terephthalate sheet.
  • a layer of ethylene-methyl acrylate-maleic anhydride terpolymer (with 20 % w/w being from methyl acrylate monomer and 0.3 % w/w being from maleic anhydride monomer) was extrusion-coated on the primed surface to form a laminated film.
  • the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 26 N/cm. After accelerated hydrothermal aging under conditions of 85 0 C and 85% RH for 1,000 hrs, the peeling strength was determined to be 11 N/cm.
  • the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
  • a 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the above-described laminated film from Example 6 has the above - described terpolymer facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 178 watts.
  • the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 12 N/cm. After accelerated hydrothermal aging under conditions of 85 0 C and 85% RH for 1,000 hrs, the peeling strength was determined to be 6 N/cm.
  • the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
  • EVA encapsulation film 500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the above-described laminated film from Example 7 has the above - described terpolymer facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 175 watts.
  • Example 8 A layer of a 25 micron-thick TedlarTM polyfluoroethylene film purchased from DuPont was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont.
  • the adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan.
  • the adhesive layer was 12 microns thick.
  • Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.50 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, two layers of ethylene copolymer were extrusion-coated on the primed surface to form a laminated film: one layer is an ethylene-methyl acrylate copolymer (with 20 % w/w being from methyl acrylate monomer), and another layer is an ethylene-methyl acrylate copolymer (with 6 % w/w being from methyl acrylate monomer) containing 5 % titanium dioxide and 1 % silicon dioxide.
  • the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 22 N/cm. After accelerated hydrothermal aging under conditions of 85 0 C and 85% RH for 1,000 hrs, the peeling strength was determined to be 18 N/cm. By using the above-described method, the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 48 N/cm.
  • Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
  • the above-described laminated film from Example 8 has the above- described copolymer facing the above-described EVA film.
  • the output power of the assembled solar cells was determined to be 178 watts.
  • the laminated film of the present invention has improved bonding strength between its film layers, and, therefore, can resist delamination.
  • the laminated film of the present invention is used for making the back sheet of a solar module, the back sheet will have improved bonding strength with the encapsulation layer.
  • solar modules that use the laminated film of the present invention as the back sheet not only have extended service life, but also have improved barrier properties to prevent oxygen and moisture from penetrating into the entire solar module, thus yielding very good results.

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Abstract

Disclosed is a laminated film having: (a) a substrate; and (b) a bonding layer of ethylene polymer on one major surface of the substrate wherein the bonding layer is placed directly on the substrate or there is a (c) primer layer between the substrate and bonding layer. Also disclosed is a solar module made of such a laminated polymer film.

Description

TITLE LAMINATED POLYMER FILM AND SOLAR MODULE MADE THEREOF
FIELD OF THE INVENTION The present invention relates to a laminated polymer film with improved bonding strength between individual film layers. The laminated polymer film not only has improved bonding strength between individual film layers, but also has improved bonding strength with an ethylene-vinyl acetate copolymer that serves as an encapsulant for solar cell components. The present invention also relates to a solar module made of such a laminated polymer film.
BACKGROUND
With global warming, governments around the world are becoming more and more demanding on energy conservation and emission reduction. Therefore, finding new energy sources to replace fossil fuels has become an urgent issue to resolve.
Solar energy is a clean, pollution-free and inexhaustible energy source. At present, solar energy is utilized primarily via its conversion into electricity by solar modules. The electricity is then used to power electric water heaters, electric vehicles, and satellite components.
A solar module refers to a photovoltaic device generating electricity directly from light, particularly, from sunlight. At present, common examples of solar modules include modules that accommodate crystalline silicon solar cells such as monocrystalline silicon solarcells, polycrystalline silicon solar cells, and nano-silicon solar cells, and thin-film solar cells such as non-crystalline thin-film silicon solar cells, cadmium telluride thin-film solar cells, and copper indium gallium selenide thin-film solar cells.
A crystalline silicon solar module mainly comprises a back sheet, an encapsulant, a photovoltaic circuit and a front sheet. The structure of a thin- film solar cell mainly comprises a photovoltaic circuit placed on a substrate (for example, a glass sheet, polymer sheet or stainless steel sheet), an encapsulant placed on the other surface of the photovoltaic circuit and the substrate, and a front sheet or back sheet placed on the encapsulant. The encapsulant is used in solar modules to bond the front sheet, the photovoltaic circuit and/or the back sheet together. In a lamination operation carried out at about 150 0C, a molten encapsulant flows into voids in a solar cell to encapsulate the solar cell. At present, commonly used encapsulation materials include ethylene -vinyl acetate copolymers and ionic polymers. However, ionic polymers have disadvantages, including high prices, difficulties in processing and very high hardness. In contrast, ethylene-vinyl acetate copolymers (EVA) have advantages of ease of processing, moderate prices and appropriate flexibility. Therefore, they are the most commonly used polymeric encapsulation materials at present.
The primary role of the front sheet in a solar module is to protect solar cells against mechanical impact and weathering. In order to make full use of the incident light, the front sheet must have a high light transmittance in a certain range of the spectrum (e.g., from 400 to 1,100 nm for crystalline silicon solar cells). The front sheet of prior art solar modules is mainly formed of glass (usually low-iron, tempered flint glass with a thickness of 3 to 4 mm) or polymeric materials.
The primary role of the back sheet in a solar module is to protect the solar cells and the encapsulant against moisture and oxidation. During the process of assembling a solar module, the back sheet is also used as a mechanical shield to prevent scratches and serves as an insulator. Therefore, the back sheet is required to have excellent moisture barrier properties and flexibility, and a good bonding strength with the encapsulant to prevent oxygen and moisture from penetrating into the solar module. A common back sheet of a solar module is a multi-layer laminated film, mainly comprising a substrate (e.g., a polyester substrate) and a bonding layer on one surface of the substrate.
Although the above-described laminated film has excellent moisture and oxygen barrier properties, the bonding strength between the substrate (e.g., a polyester substrate) and the bonding layer is not completely satisfactory.
Sometimes, delamination may take place at the interface between the two layers. Moreover, the bonding strength between the bonding layer and the encapsulant such as ethylene-vinyl acetate copolymer is also not completely satisfactory. There is still room for improvement.
Therefore, there is a need to provide a laminated film, which has excellent moisture and oxygen barrier properties, excellent bonding strength between its layers, excellent bonding strength with the layer of polyethylene-vinyl acetate resin that serves as an encapsulant for solar cells, and minimizes the use of adhesives and organic solvents.
SUMMARY
Provided is a laminated film that has excellent moisture and oxygen barrier properties, excellent bonding strength between its film layers, and excellent bonding strength with an ethylene-vinyl acetate copolymer that serves as an encapsulant. Also provided is a crystalline silicon solar module that utilizes the laminated film of the present invention for its back sheet.
Also provided is a thin-film solar module that utilizes the laminated film of the present invention for its back sheet or front sheet.
Thus, provided is a laminated film, which comprises: (a) a polyester substrate having a first surface and a second surface comprising polymers selected from the group consisting of polyC2-6 alkylene phthalates, PoIyC2-O alkylene naphthalates, and mixtures or blends thereof;
(b) an adhesive layer on the first surface of the polyester substrate;
(c) a primer layer on the second surface of the polyester substrate, wherein the primer layer is less than 0.99 micron thick;
(d) a bonding layer on the primer layer, wherein the bonding layer comprises a copolymer of ethylene and one or more monomers selected from the group consisting of Ci_4 alkyl acrylates, Ci_4 alkyl methacrylates, methacrylic acid, glycidyl methacrylate, and maleic anhydride; and (e) a protective layer on the adhesive layer comprising a fluoropolymer with a tensile modulus of greater than 150 Kpsi.
Provided is a solar module, which comprises a front sheet, a back sheet and a photovoltaic circuit that is encapsulated with an ethylene-vinyl acetate copolymer material, wherein the back sheet is made of the laminated film of the present invention.
Provided is a solar module, which comprises a photovoltaic circuit placed on a glass sheet, polymer sheet or stainless steel sheet, and a front sheet and/or a back sheet made of the laminated film of the present invention.
DETAILED DESCRIPTION
Substrate
The laminated film of the present invention includes a substrate, wherein the substrate material is selected from polyesters or fluorine-containing polymers. A laminated film may comprise a single layer or multiple layers of polyester and a single layer or multiple layers of fluorine-containing polymer, for example, a laminated film of two layers or multiple layers of polyester and fluorine- containing polymer. In another embodiment, there is a coat of metal, metal oxide and/or non-metal oxide on the polyester or fluorine-containing polymer substrate.
Therefore, in embodiments according to the present invention, the substrate may be selected from:
(i) polyesters, for example, polyC2-6 alkylene phthalates, polyC2-6 alkylene naphthalates, or binary copolymers, polybasic polymers or mixtures thereof; (ii) fluorine-containing polymers;
(iii) polyesters or fluorine-containing polymers with a coat of metal or metal oxide/non-metal oxide on the surface; or
(iv) a laminated film made from two or more materials found above.
Polyester substrate
When polyesters are used for making substrates, there are no specific restrictions to the polyesters. It may be any polyester film known in the art. It may also be a laminated double-layer or multi-layer polyester film. In one embodiment, the total thickness of the polyester substrate is 30-350 microns, preferably 50-300 microns, and more preferably 70-250 microns.
Non-restrictive examples of polyester material suitable for the substrate include, for example, polyC2-6 alkylene phthalates, preferably polyC2-4 alkylene phthalates, such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene o-phthalate, polytrimethylene o-phthalate, polybutylene o-phthalate, and polyhexylene o-phthalate, preferably polyethylene terephthalate; polyC2-6 alkylene naphthalates, preferably PoIyC2-4 alkylene naphthalates, such as polyethylene naphthalate, polytrimethylene naphthalate, and polybutylene naphthalate; and copolymers and blends of two or more above materials.
Suitable polyester substrate may be formed by film-casting and then treating by biaxial orientation to further improve mechanical strength and gas barrier properties. The film has good mechanical, dielectric, and gas barrier properties.
Suitable polyester substrates may also be purchased from the market, for example, polyethylene terephthalate sheets of various thicknesses may be purchased from E. I. du Pont de Nemours and Company, Wilmington, DE, USA ("DuPont").
Fluorine-containing polymer substrate
There are no specific restrictions to the fluorine-containing polymers suitable for making the substrate. It may be a polymer film formed by any fluorine-containing polymer known in the art. Non-restrictive examples of suitable fluorine-containing polymers include polymers of fluoroethylene; copolymers of fluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of vinylidene fluoride; copolymers of vinylidene fluoride with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of chlorotrifluoroethylene; copolymers of chlorotrifluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of tetrafluoroethylene; and copolymers of tetrafluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers.
Non-restrictive examples of the other non-fluorinated, partially-fluorinated or perfluorinated monomers include, for example, ethylene, propylene, fluoroethylene, ethylene fluoride, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, tetrafluoroethylene, perfluoroalkoxyvinyl ether, perfluoropropylene and the like. Suitable fluorine-containing polymers for the substrate may also be purchased from the market, for example, it may be a Tedlar™ polyfluoroethylene purchased from DuPont, or polyvinylidene fluorides, ethylene -tetrafluoroethylene copolymers or tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymers purchased from Dyneon LLC (Oakdale, Minn.).
The fluorine-containing polymer substrate may also be a laminated film of double-layer or multi-layer fluorine-containing polymer. In one embodiment, the substrate is a laminated film formed from a layer of polyfluoroethylene and a layer of polyvinylidene fluoride, ethylene -tetrafluoroethylene copolymer or tetrafluoroethylene-hexafluoropropylene/vinylidene fluoride copolymer.
The total thickness of the fluorine-containing polymer substrate is 20-350 microns, preferably 20-300 microns, and more preferably 20-250 microns.
Polyester or fluorine-containing polymer substrate with a coat of metal, metal oxide and/or non-metal oxide on its surface
On one or two major surfaces of the above-described polyester substrate or fluorine-containing polymer substrate is coated a single layer or multiple layers of a surface coat selected from metal, metal oxide and non-metal oxide. The surface coated substrate forms a polyester metal-coated substrate or a fluorine-containing metal-coated polymer substrate.
There are no specific restrictions to the suitable metal oxide or non-metal oxide. It may be any metal oxide or non-metal oxide commonly used in the art. In one embodiment, the metal oxide or non-metallic oxide used includes silicon oxide (SiOx, x = 1-2) or aluminum oxide (AlOx, x = 0.5-1.5). Such an oxide layer is usually deposited by using a chemical vapor deposition (CVD) method on the surface of the polyester or fluorine-containing polymer. The thickness of the oxide layer is usually 50 to 4000 A, preferably 100 to 1000 A.
There are no specific restrictions to the suitable metal coat. It may be any metal coat commonly used in the art, for example, a silver foil, an aluminum foil, or a tin foil. An aluminum foil is usually used when cost and other factors are in consideration. There are no specific restrictions to the thickness of the metal coat. It may be any thickness conventionally used in the art. In one embodiment, a metal coat is used with a thickness of 5-50 microns, preferably 7-25 microns.
A metal coat (e.g., aluminum foil) may be laminated on the polyester or fluorinated polymer substrate by using any methods known in the art. For example, an adhesive may be used to facilitate the lamination process.
The total thickness of the polyester substrate or fluorine-containing polymer substrate that has a metal or metal oxide/non-metal oxide coat on the surface is 8-350 microns, preferably 10-300 microns, and more preferably 12-250 microns.
Laminated film polyester substrate
The laminated substrate of the present invention may also be a laminated film made of a polyester and a fluorine-containing polymer. It may be a laminated film made from a single layer or multiple layers of polyester and a single layer or multiple layers of fluorine-containing polymer. The polyester is the same polyester material as what was described with the polyester substrate above. It may be a laminate made from a single layer of polyester material or multiple layers of polyester material. In one embodiment, on one or two major surfaces of the polyester layer, a layer of the above described fluorine-containing polymer is laminated.
In another embodiment, the laminate of polyester- fluorine-containing polymer is formed by alternate polyester layers and fluorine-containing polymer layers. The polyester layer is a laminate made from a single layer of polyester, or two layers, or multiple layers of polyester. The laminate of fluorine-containing polymer may be a single layer of fluorine-containing polymer, or two layers, or multiple layers of fluorine-containing polymer.
In the laminated film of the polyester and fluorine-containing polymer, the thickness may be any known thickness conventionally used in the art. In one embodiment, a fluorine-containing polymer layer is used with a thickness of 15-
50 microns, preferably 20-40 microns. The total thickness of the laminated film substrate of polyester- fluorine- containing polymer is 30-350 microns, preferably 50-300 microns, and more preferably 70-250 microns.
The method of laminating the polyester layer with the fluorine-containing polymer layer may be any conventional method known in the art. In one embodiment, an adhesive is used for bonding the fluorine-containing polymer layer to the polyester substrate.
There are no specific restrictions for the adhesives for bonding the fluorine-containing polymer layer to the polyester layer. They may be any conventional adhesives known in the art. In one embodiment, a polyurethane adhesive is used, which is formed by mixing PP5250 and 15200 adhesives manufactured by Mitsubishi of Japan according to a ratio of 8-10:1 by weight, preferably 9:1.
There are no specific restrictions to the thickness of the adhesive layer for bonding the fluorine-containing polymer to the polyester, as long as the adhesion strength can meet the requirements. In one embodiment, the thickness of the adhesive layer is in the range of 1-30 microns, preferably 5-25 microns, and more preferably 8-18 microns.
In one embodiment, a laminated film of two layers or multiple layers of polyester/fluorine-containing polymer is used as a substrate. The laminated film is selected from the group consisting of polyfluoroethylene/poly ethylene terephthalate laminated film, polyvinylidene fluoride/polyethylene terephthalate laminated film, polyfluoroethylene/polyethylene naphthalate laminated film, polyfluoroethylene/polyethylene terephthalate/polyfluoroethylene laminated film, and polyethylene terephthalate/polyethylene terephthalate/polyethylene terephthalate laminated film.
In another embodiment, a single-layer or multi-layer laminated film comprising a layer of aluminum foil with a thickness of 3-50 microns is used as a substrate. Non-restrictive examples of the substrate include, for example, polyfluoroethylene/aluminum foil/polyethylene terephthalate. The aluminum foil may be bonded with an adhesive on the surface of fluorine-containing polymer or polyester. In another embodiment, a polyester film with a metal oxide coat on its surface is used as a substrate. Non-restrictive examples of the substrate include, for example, polyfluoroethylene/aluminum oxide/polyethylene terephthalate/poly ethylene terephthalate . The substrate may contain various types of additives, such as photo- stabilizers, thermal stabilizers, hydrolysis resistant agents, surface modifiers, fluorescent brightening agents, light reflecting agents, dyes, and pigments. Particular suitable additives are commonly used additives in the art. When the substrate is a laminated film (for example, polyester laminated film or laminated film of polyester- fluorine-containing polymer), the additives may optionally be added into each layer of the laminated film.
There are no specific restrictions to the content of the additives as long as the additives do not produce an adverse impact on the substrate or strength of the laminated film.
Bonding layer
The laminated film comprises a bonding layer on one major surface of the substrate for bonding the back sheet to the encapsulant of ethylene-vinyl acetate copolymer. Suitable materials used for forming the bonding layer are ethylene copolymer materials, which are selected from the following groups: ethylene-Ci_4 alkyl methacrylate copolymers and ethylene-Ci_4 alkyl acrylate copolymers, for example, ethylene-methyl methacrylate copolymers, ethylene -methyl acrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-propyl methacrylate copolymers, ethylene -propyl acrylate copolymers, ethylene -butyl methacrylate copolymers, ethylene-butyl acrylate copolymers, and mixtures of two or more copolymers thereof, wherein copolymer units resulting from ethylene account for 50%-99%, preferably 70%-95%, by total weight of each copolymer; ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, and blends thereof, wherein copolymer units resulting from ethylene account for 50-99%, preferably 70-95%, by total weight of each copolymer; ethylene -maleic anhydride copolymers, wherein copolymer units resulted from ethylene account for 50-99%, preferably 70-95%, by total weight of the copolymer; polybasic polymers formed by ethylene with at least two co-monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, ethylene -methacrylic acid, ethylene-acrylic acid and ethylene-maleic anhydride, non-restrictive examples of which include, for example, terpolymers of ethylene -methyl acrylate- methacrylic acid (wherein copolymer units resulting from methyl acrylate account for 2-30 % by weight and copolymer units resulting from methacrylic acid account for 1-30 % by weight), terpolymers of ethylene-butyl acrylate - methacrylic acid (wherein copolymer units resulting from butyl acrylate account for 2-30 % by weight and copolymer units resulting from methacrylic acid account for 1-30 % by weight), terpolymers of ethylene-propyl methacrylate- acrylic acid (wherein copolymer units resulting from propyl methacrylate account for 2-30 % by weight and copolymer units resulting from acrylic acid account for 1-30 % by weight), terpolymers of ethylene-methyl acrylate-acrylic acid (wherein copolymer units resulting from methyl acrylate account for 2-30 % by weight and copolymer units resulted from acrylic acid account for 1-30 % by weight), terpolymers of ethylene-methyl acrylate-maleic anhydride (wherein copolymer units resulting from methyl acrylate account for 2-30 % by weight and copolymer units resulting from maleic anhydride account for 0.2-10 % by weight), terpolymers of ethylene-butyl acrylate-maleic anhydride (wherein copolymer units resulting from butyl acrylate account for 2-30 % by weight and copolymer units resulted from maleic anhydride account for 0.2-10 % by weight), and terpolymers of ethylene-acrylic acid-maleic anhydride (wherein copolymer units resulting from acrylic acid account for 2-30 % by weight and copolymer units resulting from maleic anhydride account for 0.2-10 % by weight); copolymers formed by ethylene and glycidyl methacrylate with at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, ethylene-methacrylic acid, ethylene-acrylic acid, and ethylene-maleic anhydride, non-restrictive examples of which include, for example, terpolymers of ethylene- butyl acrylate-glycidyl methacrylate, wherein copolymer units resulting from butyl acrylate account for 2-30 % by weight and copolymer units resulting from glycidyl methacrylate account for 1-15 % by weight; and blends of two or more above-described materials.
The thickness of the bonding layer suitable for the laminated film is 10- 400 microns, preferably 40-200 microns.
The bonding layer may have an encapsulation layer for encapsulating the solar module (usually polyethylene-vinyl acetate, polyethylene-methyl acrylate, polyethylene-butyl acrylate, polyethylene -methacrylic acid, ion polymer, polyurethane, or polyvinyl butyral) and has good adhesion properties, good dielectric properties and aging resistance.
The bonding layer may contain various types of additives. Suitable non- restrictive examples are photo-stabilizers, thermal stabilizers, slip agents, light reflecting additives, and pigments.
There are no specific restrictions to the content of the additives in the bonding layer, as long as the additives do not produce an adverse impact on the bonding layer or final adhesion properties of the laminated film.
The bonding layer may be bonded to the substrate by using any methods known in the art. Non-restrictive examples of suitable bonding methods include, for example, melting suitable copolymer resin in an extruder and then coating the melt on the substrate surface by extrusion through an extruder die, or adhering the bonding layer to the substrate with an adhesive.
In one embodiment, the bonding layer is bonded to the substrate without the use an adhesive, particularly without the use an adhesive that is diluted with an organic solvent. In one embodiment, an ethylene-methyl acrylate copolymer (containing 13
% of methyl acrylate by weight, with a melt index of 9, manufactured by DuPont) is melted and extruded out from a single screw extruder at the temperature of 290 0C, bonding the melt to a polyethylene terephthalate (PET) substrate.
In addition, the bonding layer may be a laminate of a single-layer material or a double-layer or multi-layer material, for example, the bonding layer of the present invention may be a 2-8 layer, preferably 2-6 layer, more preferably 2-3 layer laminate of the polymer material selected respectively from above-described ethylene copolymer materials. In one embodiment, the bonding layer is a tri-layer laminate, wherein one layer is a polymer sheet formed from polymer materials selected from ethylene- Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, and ethylene-maleic anhydride copolymers. Another layer is a polymer sheet formed from a polybasic polymer of ethylene with at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride. Another layer is a polymer sheet formed from a glycidyl methacrylate-containing polybasic polymer of ethylene and glycidyl methacrylate formed from at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid and maleic anhydride. The tri-layer polymer sheet has approximately the same thickness so that the final polymer sheet that serves as a bonding layer has a thickness of 10-400 microns, preferably 40-200 microns. In another embodiment, the bonding layer is a double-layer laminate, wherein one layer is a polymer sheet formed from polymer materials selected from ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene with at least two monomers selected from Ci_4 alkyl methacrylate, ethylene-Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride; and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate and at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and blends of two or more polymers described above. Another layer is a polymer sheet formed from polymer materials selected from polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co- monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and blends of two or more polymers described above.
In another embodiment, the bonding layer is a tri-layer laminate, wherein one layer is a polymer sheet formed from polymer materials selected from ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene -methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene -maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride; and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and blends of two or more polymers described above. Another layer is a polymer sheet formed by polymer materials selected from polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co-monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, or blends of two or more polymers described above. Yet another layer is a polymer sheet formed from polymer materials selected from polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-Ci_4 alkyl methacrylate copolymers, ethylene-Ci_4 alkyl acrylate copolymers, ethylene- methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers, copolymers formed from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, and glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co- monomer selected from Ci_4 alkyl methacrylate, Ci_4 alkyl acrylate, methacrylic acid, acrylic acid, and maleic anhydride, or blends of two or more polymers described above.
The polyethylene and polypropylene suitable for the bonding layer include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, metallocene-derived low density polyethylene, and homopolypropylene.
Two or more extruders may be used for bonding the multi-layer laminated film of the bonding layer to the substrate of the present invention by extrusion- coating. In order to increase the bonding strength between the substrate and the bonding layer, the substrate surface may be surface-treated. There are no restrictions to suitable surface treatment methods, which may be any conventional methods known in the art. For example, it may be a corona treatment, flame treatment, or primer treatment. Non-restrictive examples of suitable primers include, for example, imine primers and amine primers.
When primer treatment is used for surface treatment of the substrate surface, there are no specific restrictions to the final thickness of the formed primer, which may be any thickness commonly used in the art, as long as the primer does not adversely affect the bonding strength between the polyester substrate and the bonding layer. The primer thickness is usually less than 1.5 microns, suitably less than 1.2 microns, preferably less than 1 micron, more preferably less than 0.99 microns, most preferably less than 0.8 microns, and optimally less than 0.5 microns. For example, the primer thickness can be less than 0.45 microns, less than 0.4 microns, less than 0.3 microns or less than 0.25 microns.
In one embodiment, the primer thickness is 0.01-0.99 microns, suitably 0.01-0.8 microns, preferably 0.01-0.5 microns.
When surface treatment methods such as corona treatment or flame treatment are used, the bonding layer is directly placed on the substrate. In the present invention, the phrase "bonding layer is directly placed on the substrate" refers to a situation where there is no coat or layer applied between the bonding layer and the substrate for improving the bonding strength between the two. The laminated film has high bonding or peeling strength between the substrate and the bonding layer. Compared with the bonding strength between the substrate and bonding layer found in the art, the bonding strength between the two layers of the laminated film is higher, and the bonding strength may be as high as about 10N/cm according to a T-type peeling test.
The laminated film is particularly suitable for making a back sheet of a crystalline silicon solar module or for making a front sheet or a back sheet of a thin film solar module. This type of back sheet or front sheet not only has good peeling strength, but also avoids delamination between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer due to a very high bonding strength between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer, and can effectively extend the service life of solar modules.
The present invention is further exemplified by the following illustrative examples.
EXAMPLES
Test Methods
1. Test for peeling strength between the substrate and the bonding layer of the laminated film.
A laminated film was cut into sample strips of 2.54 cm in width and 10 cm in length, and the bonding layer and the substrate were fixed respectively in the upper and lower grips of an extension meter to carry out a peeling test at a speed of 5 in/min.
2. Test of peeling strength between the bonding layer and the encapsulant of ethylene-vinyl acetate copolymer
A laminated film (with the bonding layer adjacent to the encapsulation film), an encapsulation film of ethylene-vinyl acetate copolymer and a piece of glass were stacked in a proper order and placed in a laminating press for cross- linking for 15 min under an operation temperature of 140 0C. Then, the sample was cut into strips of 2.54 cm in width and 10 cm in length. The laminated film of the back sheet and the encapsulant/glass layer were fixed respectively in the upper and lower grips of an extension meter to carry out a peeling test at a speed of 5 in/min.
3. Hydrothermal aging test for solar cell components The process for encapsulating solar cell components includes sorting the solar cells, single welding, serial welding, stacking, laminating, component testing, framing and cleaning. The hydrothermal aging test of laminated solar cell components was carried out in a climatic chamber VC4018 (purchased from Vόtsch Industrietechnik GmbH, Germany) according to Clause 10.13 of IEC 61215 Standard. Solar cell components for testing were maintained for 1,000 hrs under the hydrothermal conditions (85 0C and 85% relative humidity). Then, the components were taken out, and the encapsulation layer of ethylene-vinyl acetate copolymer was peeled off. The peeled encapsulation layer of ethylene-vinyl acetate copolymer was tested for its yellowing index, ΔYI, on a Lambda 950 UV/visible/Near-IR spectrophotometer (including a 150 mm integrating sphere) from Perkin Elmer, U.S.A.:
ΔYI = Y1 - Y0 where Yo is the value of extinction of the encapsulation layer of ethylene-vinyl acetate copolymer peeled without being treated under the hydrothermal conditions, measured with a Lambda 950 UV/visible/Near-IR spectrophotometer. Y1 is the value of extinction of the encapsulation layer of ethylene-vinyl acetate copolymer peeled after being treated under the hydrothermal conditions, which was also measured with a Lambda 950 UV/visible/Near-IR spectrophotometer. If the index equals zero, it means that the encapsulant was not influenced by outside oxygen and moisture when placed under the hydrothermal conditions. In other words, the solar cell has excellent air tightness. Therefore, the smaller the index, the better.
4. Testing method for solar cell output power Solar cell output power was determined by using a 3500 SLP component testing system (purchased from Spire Corporation, U.S.A.). It was compared with polycrystalline silicon solar cells assembled from ordinary front and back sheet materials. 5. Testing method of bonding strength of a bonding layer between layers of a laminated film
A laminated film was cut into sample strips of 2.54 cm in width and 10 cm in length, and the top layer and the bottom layer were fixed respectively in the upper and lower grips of an extension meter to carry out a peeling test at a speed of 5 in/min.
Comparative Example 1 In this example, a back sheet made of a laminate film with a structure of
PVF/PET/PVF purchased from Isovolta Group was used. PVF is an abbreviation for 'polyvinylidene fluoride.'
By using the above-described method, the peeling strength between PVF and PET was determined to be 4 N/cm. By using the above-described method, the peeling strength between the back sheet and the EVA encapsulation layer after lamination was determined to be
4.5 N/cm.
Preparing a solar module The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar
Glass Co., Ltd.;
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); and
A back sheet made of the above-described laminated film from
Comparative Example 1. By using the above-described method, the output power of the assembled solar cells was determined to be 175 watts.
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the yellowing index ΔYI was determined to be 0.6.
Example 1
Preparing a laminated film and testing properties thereof
A layer of a 25 micron-thick Tedlar™ polyfluoroethylenefϊlm purchased from E. I. du Pont de Nemours and Company, Wilmington, DE, USA ("DuPont"), was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that is also purchased from DuPont. The adhesive used was a 9: 1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan. The adhesive layer was 12 microns thick. On an extrusion-coating machine manufactured by Davis Standard,
Epomin P- 1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.90 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-methacrylate copolymer (with 80% being from ethylene monomer) was extrusion-coated at 290 0C on the primed surface with a thickness of 75 microns to form a laminated film.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the ethylene-methacrylate copolymer layer was determined to be 21 N/cm. Compared with the peeling strength of the conventional laminated film discribed in Comparative Example 1 , the laminated film of the present invention is increased 4 fold.
After accelerated hydrothermal aging under conditions of 85 0C and 85% RH (relative humidity) for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
By using the above-described method, the peeling strength between the ethylene-methacrylate copolymer layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 81 N/cm. Compared with the peeling strength between the conventional laminated film (Comparative Example 1) and the ethylene-vinyl acetate copolymer encapsulant, the peeling strength between the laminated film of this example and the ethylene-vinyl acetate copolymer encapsulant is increased by about 16 fold.
Preparing a solar module The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); and
The above-described laminated film from Example 1 has the above- described ethylene -methacrylate copolymer facing the above-described EVA film. By using the above-described method, the output power of the assembled solar cells was determined to be 177 watts.
Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result of the yellowing index ΔYI was 0.1.
Comparative Example 2
PET, as described in Example 1 of JP2008-108947,and an ethylene- methacrylate copolymer, as described in Example 1 of JP2008-108947, were laminated by thermocompression, and then the peeling strength between them was tested. The initial peeling strength was 1.5 N/cm. After accelerated hydrothermal aging for 1,000 hrs, the peeling strength was less than 0.7 N/cm. Comparative Example 3
PET, as described in Example 1 of JP2008- 108947, and an ethylene- methacrylate copolymer, as described in Example 1 of JP2008- 108947, were bonded with a polyurethane adhesive (polyester-based polyurethane matrix and a mixed curing agent of isophorone diisocyanate (IPDI) and xylylene diisocyanate (XDI) . The initial peeling strength between them was 7.5 N/cm. After accelerated hydrothermal aging, the peeling strength was less than 0.8 N/cm.
Example 2
Preparing a laminated film and testing properties thereof
A layer of a 25 micron-thick Tedlar™ polyfluoroethylene film purchased from DuPont was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont. The adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan. The adhesive layer was 12 microns thick.
On an extrusion-coating machine manufactured by Davis Standard, Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.50 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-methacrylate copolymer (with 80% w/w being from ethylene monomer) containing 5% (w/w) of titanium dioxide additive by total weight of the copolymer was extrusion-coated at 290 0C on the primed surface to form a laminated film with a thickness of 75 microns.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the ethylene-methacrylate copolymer layer was determined to be 20 N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85% RH for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
By using the above-described method, the peeling strength between the ethylene-methacrylate copolymer layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm. Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.); and
The above-described laminated film from Example 2 (with the above- described ethylene-methacrylate copolymer facing the above-described
EVA film).
By using the above-described method, the output power of the assembled solar cells was determined to be 177 watts.
Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result for the yellowing index ΔYI was 0.1.
Example 3
Preparing a laminated film and testing properties thereof
A layer of a 25 micron-thick Tedlar™ polyfluoroethylene film purchased from DuPont was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont. The adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan. The adhesive layer is 12 microns thick.
On an extrusion-coating machine manufactured by Davis Standard, Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.45 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a 1 :9 (w/w) mixture of ethylene -maleic anhydride copolymer (with 80% w/w being from ethylene monomer) and ethylene-methacrylate copolymer (with 80% w/w being from ethylene monomer) containing 5% (w/w) of titanium dioxide additive by total weight of the copolymer mixture was extrusion-coated on the primed surface to form a laminated film with a thickness of 75 microns.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 23 N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85% RH for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
By using the above-described method, the peeling strength between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer was determined to be 80 N/cm.
Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar
Glass Co., Ltd.; - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); and
The above-described laminated film from Example 3 has the above- described copolymer mixture facing the above-described EVA film. By using the above-described method, the output power of the assembled solar cells was determined to be 178 watts. Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result of the yellowing index ΔYI was 0.1.
Example 4
A layer of a 25 micron-thick Tedlar™ polyfluoroethylene film purchased from DuPont was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont. The adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan. The adhesive layer was 12 microns thick.
On an extrusion-coating machine manufactured by Davis Standard, Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.48 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-butyl acrylate-methacrylic acid terpolymer (the ratio of the three monomer units is 88.5: 7.5: 4 by weight) was extrusion-coated on the primed surface to form a laminated film with a thickness of 75 microns.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 25 N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85% RH for 1,000 hrs, the peeling strength was determined to be 12 N/cm.
By using the above-described method, the peeling strength between the bonding layer and the encapsulation layer of ethylene-vinyl acetate copolymer was determined to be 82 N/cm.
Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.); and
The above-described laminated film from Example 4 has the above- described terpolymer facing the above-described EVA film. By using the above-described method, the output power of the assembled solar cells was determined to be 175 watts.
Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result for the yellowing index ΔYI was 0.1.
Example 5
A layer of a 25 micron-thick Tedlar™ polyfluoroethylene film purchased from DuPont was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont. The adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from
Mitsubishi, Japan. The adhesive layer was 12 microns thick.
On an extrusion-coating machine manufactured by Davis Standard,
Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.48 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-butyl acrylate-glycidyl methacrylate terpolymer
(with 25 % w/w being from butyl acrylate monomer and 12 % w/w being from glycidyl methacrylate monomer) was extrusion-coated on the primed surface to form a laminated film.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 26
N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85%
RH for 1,000 hrs, the peeling strength was determined to be 11 N/cm. By using the above-described method, the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar
Glass Co., Ltd.; - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); and
The above-described laminated film from Example 5 has the above- described terpolymer facing the above-described EVA film. By using the above-described method, the output power of the assembled solar cells was determined to be 178 watts.
Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result for the yellowing index ΔYI was 0.1.
Example 6
A layer of a 25 micron-thick Tedlar™ polyfluoroethylene film purchased from DuPont, was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont. The adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan. The adhesive layer was 12 microns thick. On an extrusion-coating machine manufactured by Davis Standard, Epomin P- 1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.5 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, a layer of ethylene-methyl acrylate-maleic anhydride terpolymer (with 20 % w/w being from methyl acrylate monomer and 0.3 % w/w being from maleic anhydride monomer) was extrusion-coated on the primed surface to form a laminated film.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 26 N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85% RH for 1,000 hrs, the peeling strength was determined to be 11 N/cm.
By using the above-described method, the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar Glass Co., Ltd.;
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series);
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); and
The above-described laminated film from Example 6 has the above - described terpolymer facing the above-described EVA film.
By using the above-described method, the output power of the assembled solar cells was determined to be 178 watts. Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result for the yellowing index ΔYI was 0.1.
Example 7
A major surface of a 200 micron-thick polyethylene terephthalate sheet purchased from DuPont was corona-treated.
On an extrusion-coating machine manufactured by Davis Standard, a layer of ethylene -methyl acrylate-maleic anhydride terpolymer (with 20 % w/w being from methyl acrylate monomer and 0.3 % w/w being from maleic anhydride monomer) was extrusion-coated on the corona-treated surface of the polyethylene terephthalate sheet to form a laminated film.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 12 N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85% RH for 1,000 hrs, the peeling strength was determined to be 6 N/cm.
By using the above-described method, the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 80 N/cm.
Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module: - A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar
Glass Co., Ltd.;
EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); - Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material Co., Ltd.); and
The above-described laminated film from Example 7 has the above - described terpolymer facing the above-described EVA film.
By using the above-described method, the output power of the assembled solar cells was determined to be 175 watts.
Hydrothermal aging test on solar cell components By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result for the yellowing index ΔYI was 0.1.
Example 8 A layer of a 25 micron-thick Tedlar™ polyfluoroethylene film purchased from DuPont was bonded on a major surface of a 200 micron-thick polyethylene terephthalate sheet that was also purchased from DuPont. The adhesive used was a 9:1 (w/w) mixture of PP5250/I5200 polyurethane adhesive purchased from Mitsubishi, Japan. The adhesive layer was 12 microns thick. On an extrusion-coating machine manufactured by Davis Standard,
Epomin P-1050 (made by Nippon Shokubai Co., Ltd.) was coated as a 0.50 micron-thick primer on another major surface of the polyethylene terephthalate sheet. Then, two layers of ethylene copolymer were extrusion-coated on the primed surface to form a laminated film: one layer is an ethylene-methyl acrylate copolymer (with 20 % w/w being from methyl acrylate monomer), and another layer is an ethylene-methyl acrylate copolymer (with 6 % w/w being from methyl acrylate monomer) containing 5 % titanium dioxide and 1 % silicon dioxide.
By using the above-described method, the peeling strength between the polyethylene terephthalate sheet and the bonding layer was determined to be 22 N/cm. After accelerated hydrothermal aging under conditions of 85 0C and 85% RH for 1,000 hrs, the peeling strength was determined to be 18 N/cm. By using the above-described method, the peeling strength between the bonding layer and the ethylene-vinyl acetate copolymer encapsulant was determined to be 48 N/cm.
Preparing a solar module
The following components were stacked in the following order and then laminated by thermocompression under vacuum to form a solar module:
A 3.2 mm-thick tempered glass purchased from Dongguan CSG Solar
Glass Co., Ltd.; - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.);
Polycrystalline silicon photovoltaic circuits (125 x 125 x 0.3 mm, 72 circuits in series); - EVA encapsulation film (500 micron, Ruifu brand EVA film for making photovoltaic cells, R767, purchased from Ruiyang Photovoltaic Material
Co., Ltd.); and
The above-described laminated film from Example 8 has the above- described copolymer facing the above-described EVA film. By using the above-described method, the output power of the assembled solar cells was determined to be 178 watts.
Hydrothermal aging test on solar cell components
By using the above-described method to carry out a hydrothermal aging test of the solar cell components, the calculated result for the yellowing index ΔYI was 0.1.
It can be seen from the above-described test results that the laminated film of the present invention has improved bonding strength between its film layers, and, therefore, can resist delamination. When the laminated film of the present invention is used for making the back sheet of a solar module, the back sheet will have improved bonding strength with the encapsulation layer. As a result, solar modules that use the laminated film of the present invention as the back sheet not only have extended service life, but also have improved barrier properties to prevent oxygen and moisture from penetrating into the entire solar module, thus yielding very good results.

Claims

CLAIMSWhat is claimed is:
1. A laminated film comprising:
(a) a polyester substrate having a first surface and a second surface comprising polymers selected from the group consisting of polyC2-6 alkylene phthalates,
PoIyC2-O alkylene naphthalates, and mixtures or blends thereof;
(b) an adhesive layer on the first surface of the polyester substrate;
(c) a primer layer on the second surface of the polyester substrate, wherein the primer layer is less than 0.99 micron thick; (d) a bonding layer on the primer layer, wherein the bonding layer comprises a copolymer of ethylene and one or more monomers selected from the group consisting of Ci_4 alkyl acrylates, Ci_4 alkyl methacrylates, methacrylic acid, acrylic acid, glycidyl methacrylate, and maleic anhydride; and (e) a protective layer on the adhesive layer comprising a fluoropolymer with a tensile modulus of greater than 150 Kpsi.
2. The laminated film of Claim 1, wherein the polyester substrate further comprises a coat of metal, metal oxide, or non-metal oxide.
3. The laminated film of Claim 1, characterized in that the polyC2-6 alkylene phthalate is selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene o-phthalate, polytrimethylene o- phthalate, polybutylene o-phthalate and polyhexylene o-phthalate, and the PoIyC2- 6 alkylene naphthalate is selected from the group consisting of polyethylene naphthalate, polytrimethylene naphthalate and polybutylene naphthalate.
4. The laminated film of Claim 1, wherein the fluorine-containing polymer is selected from the group consisting of polymers of fluoroethylene; copolymers of fluoroethylene with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of vinylidene fluoride; copolymers of vinylidene fluoride with other non-fluorinated, partially-fluorinated or perfluorinated monomers; polymers of chlorotrifluoroethylene; copolymers of chlorotrifluoroethylene with other non-fluorinated, partially- fluorinated or perfluorinated monomers; polymers of tetrafluoroethylene; and copolymers of tetrafluoroethylene with other non-fluorinated, partially- fluorinated or perfluorinated monomers.
5. The laminated film of Claim 4, wherein the other non-fluorinated, partially-fluorinated or perfluorinated monomers are selected from the group consisting of ethylene, propylene, fluoroethylene, ethylene difluoride, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, tetrafluoroethylene, perfluoroalkoxyvinyl ether and perfluoropropylene.
6. The laminated film of Claim 1, wherein the polyester substrate comprises:
(a) a layer comprising copolymers selected from the group consisting of polyC2-6 alkylene phthalates, polyC2-6 alkylene naphthalates, and mixtures or blends thereof; and
(b) a layer comprising polyfluoroethylene or polyvinylidene fluoride.
7. The laminated film of Claim 1, wherein the bonding layer comprises a copolymer of ethylene and one or more monomers selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, glycidyl methacrylate and maleic anhydride.
8. The laminated film of Claim 7, wherein the ethylene is 50-99 % by weight based on the total weight of the copolymer.
9. The laminated film of Claim 1, wherein the copolymer of the bonding layer is selected from ethylene-methyl acrylate-methacrylic acid terpolymers, ethylene-butyl acrylate-methacrylic acid terpolymers, ethylene -propyl methacrylate-acrylic acid terpolymers, ethylene-butyl acrylate-glycidyl methacrylate terpolymers, and ethylene-methyl acrylate -maleic anhydride terpolymers.
10. The laminated film of Claim 9, wherein the copolymer is an ethylene - butyl acrylate-glycidyl methacrylate terpolymer and butyl acrylate is 2-30 % by weight, and glycidyl methacrylate accounts for 1-15 % by weight based on the weight of the terpolymer.
11. The laminated film of Claim 1 , wherein the bonding layer has a thickness of 10-400 microns.
12. The laminated film of Claim 1, wherein the bonding layer is extrusion-coated on the substrate.
13. The laminated film of Claim 1, wherein the bonding layer is a single layer of a copolymer of ethylene and one or more monomers selected from the group consisting of Ci_4 alkyl acrylates, Ci_4 alkyl methacrylates, methacrylic acid, glycidyl methacrylate, and maleic anhydride.
14. The laminated film of Claim 1, wherein the bonding layer is a 2-8 layer laminate, wherein each layer of the laminate is a copolymer of ethylene and one or more monomers selected from the group consisting of Ci_4 alkyl acrylates, Ci_4 alkyl methacrylates, methacrylic acid, glycidyl methacrylate, and maleic anhydride.
15. The laminated film of Claim 1, wherein the bonding layer further comprises one or more polymer sheets formed by polymer materials selected from polyethylene; polypropylene; ethylene-propylene copolymers; ethylene-Ci_4 alkyl methacrylate copolymers; ethylene-methacrylic acid copolymers; ethylene -maleic anhydride copolymers; copolymers derived from ethylene and at least two monomers selected from Ci_4 alkyl methacrylate, methacrylic acid and maleic anhydride; glycidyl methacrylate-containing copolymers formed from ethylene and glycidyl methacrylate with at least one co-monomer selected from Ci_4 alkyl methacrylate, methacrylic acid and maleic anhydride; and blends thereof, wherein the polyethylene is selected from high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, metallocene-derived low density polyethylene, and the polypropylene is homopolypropylene.
16. The laminated film of Claim 1, wherein the primer layer comprises an imine or amine type of primer.
17. The laminated film of Claim 1, wherein the adhesive layer comprises polyurethane.
18. A solar cell module comprising, in order of position from a front sun- facing side to a back non-sun-facing side, (a) a front sheet, (b) one or more solar cells that are encapsulated with a polymeric material, and (c) a back sheet, wherein one or both of the front and back sheet is made of the laminated film of Claim 1.
19. The solar cell module of Claim 18, wherein the solar cell(s) are encapsulated with ethylene -vinyl acetate copolymer, and wherein the back sheet is made of the laminated film of Claim 1.
20. The solar cell module of Claim 18, wherein the solar cell(s) are selected from monocrystalline silicon solar cells, polycrystalline silicon solar cells and nano-silicon solar cells.
21. A thin- film solar cell module, comprising:
(a) thin-film solar cell(s) deposited on a glass sheet, polymer sheet or stainless steel sheet;
(b) a polymeric encapsulant laminated on the thin-film solar cell(s) ; and (c) a back sheet or a front sheet laminated on the encapsulant, wherein the back sheet or front sheet is made of the laminated film as described in Claim 1.
22. The thin-film solar cell module of Claim 21, wherein the polymeric encapsulant comprises ethylene vinyl acetate copolymer.
23. The thin-film solar cell module of Claim 22, wherein the thin-film solar cell(s) are selected from non-crystalline thin-film silicon solar cells, cadmium telluride thin-film solar cells, and copper indium gallium selenide thin- film solar cells.
EP09789931A 2009-03-03 2009-06-24 Laminated polymer film and solar module made thereof Withdrawn EP2403713A1 (en)

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Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120006407A1 (en) * 2009-03-26 2012-01-12 Lintec Corporation Protective sheet for solar cell module and solar cell module including the same
US20100294363A1 (en) * 2009-05-22 2010-11-25 Mitsubishi Polyester Film, Inc. Coated Polyester Film For Lamination to Ethylene-Vinyl Acetate Layers
JP5947209B2 (en) * 2009-06-09 2016-07-06 エスケーシー カンパニー，リミテッド Black sheet and manufacturing method thereof
TW201109350A (en) * 2009-07-31 2011-03-16 Du Pont Cross-linkable encapsulants for photovoltaic cells
JP2013537494A (en) * 2010-07-30 2013-10-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Multilayer film comprising a fluorinated copolymer resin layer and a sealing layer
JP5820132B2 (en) * 2011-03-09 2015-11-24 株式会社ブリヂストン Solar cell sealing film and solar cell using the same
KR101371856B1 (en) * 2011-03-17 2014-03-10 주식회사 엘지화학 Environmentally friendly backsheet for solar cell and preparation method thereof
JP5623952B2 (en) * 2011-03-25 2014-11-12 富士フイルム株式会社 SOLAR CELL POLYMER SHEET AND METHOD FOR PRODUCING THE SAME, SOLAR CELL BACK SHEET, AND SOLAR CELL MODULE
CN102815053B (en) * 2011-06-07 2015-07-15 杜邦公司 Solar cell back panel with improved cohesive property on packing materials
SG2014007892A (en) * 2011-08-04 2014-04-28 3M Innovative Properties Co Method of making delamination resistant assemblies
CN103988578B (en) 2011-08-04 2017-07-21 3M创新有限公司 The shielded barrier component in edge
CN103889717B (en) * 2011-10-21 2016-06-29 Lg化学株式会社 Multilayer film and manufacture method thereof
MX368295B (en) 2012-06-05 2019-09-27 Dow Global Technologies Llc Films containing functional ethylene-based polymer compositions.
CN103507360B (en) * 2012-06-19 2015-09-30 杜邦公司 Comprise the sandwich construction of perfluorinated polymers layer
CN102931261B (en) * 2012-10-22 2015-09-23 苏州中来光伏新材股份有限公司 A kind of photovoltaic module solar cell notacoria and processing technology thereof
CN104955857B (en) * 2012-12-24 2017-02-22 株式会社Lg化学 Copolymer
CN104760384A (en) * 2012-12-31 2015-07-08 台州市珠叶机械科技有限公司 Method for manufacturing laminated packaging material
CN105074940B (en) * 2013-02-27 2017-04-26 日本瑞翁株式会社 Solar cell module and method for manufacturing same
US10060851B2 (en) 2013-03-05 2018-08-28 Plexense, Inc. Surface plasmon detection apparatuses and methods
KR101592241B1 (en) 2013-04-15 2016-02-05 (주)플렉센스 Method of fabricating a device having an array of nano particles, surface plasmon based sensor, and method of assaying substances using the sensor
CN103311341A (en) * 2013-05-21 2013-09-18 常州回天新材料有限公司 Novel solar cell back panel and preparation method thereof
KR101487257B1 (en) * 2013-07-11 2015-01-28 엘에스산전 주식회사 Photovoltaic module
CN105706251B (en) * 2013-11-11 2018-09-25 东洋铝株式会社 Backside protective sheet used for solar batteries
KR101528901B1 (en) * 2013-12-24 2015-06-15 도레이첨단소재 주식회사 Polyester film for optical use
CN104409542B (en) * 2014-11-13 2016-08-03 无锡中洁能源技术有限公司 A kind of solar cell backboard fluorine-containing Weather-proof film and preparation method thereof
KR101604283B1 (en) * 2014-12-08 2016-03-17 엘에스산전 주식회사 Solar cell module
CN104842616B (en) * 2015-04-10 2017-08-08 苏州中来光伏新材股份有限公司 A kind of photovoltaic solar cell composite back plate and preparation method and its component
WO2017014307A1 (en) * 2015-07-23 2017-01-26 富士フイルム株式会社 Laminate
BR112018009028B1 (en) 2015-11-19 2022-07-19 Dow Global Technologies Llc POLYMER MIX AND MULTILAYER STRUCTURE
EP3185310B1 (en) 2015-12-23 2019-02-20 Agfa-Gevaert A backsheet for a solar cell module
CN106129258A (en) * 2016-08-30 2016-11-16 中国乐凯集团有限公司 Flexible solar battery encapsulation multi-layer compound film and application thereof
CN107841029B (en) * 2017-01-17 2020-08-21 湖北航天化学技术研究所 High-weather-resistance PE (polyethylene) film for solar cell back plate
CN107603008B (en) * 2017-08-25 2020-08-25 江苏精良高分子材料有限公司 Semi-dull material for BOPP semi-dull transfer base film and preparation method and application thereof
CN109776833B (en) * 2017-11-14 2021-09-24 杜邦公司 Transparent polymer film or sheet with scratch-resistant coating
US20210249548A1 (en) * 2020-01-10 2021-08-12 Dupont Electronics, Inc. Repair tape and method of repairing a damaged backsheet of solar cell module using the same
CN113122158A (en) * 2020-01-10 2021-07-16 杜邦电子公司 Repairing adhesive tape and method for repairing damaged back plate of solar cell module by using same
CN111816723B (en) * 2020-08-21 2021-12-24 苏州赛伍应用技术股份有限公司 Carrier film for photovoltaic module and photovoltaic module
CN112831291B (en) * 2020-11-05 2022-09-30 苏州赛伍应用技术股份有限公司 Packaging adhesive film with lattice structure and preparation method and application thereof
KR102484917B1 (en) * 2021-06-16 2023-01-09 (주)동해플라스틱 Adhesive coating liquid composition and building sheet manufactured by applying the same

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5053457A (en) * 1989-06-13 1991-10-01 E. I. Du Pont De Nemours And Company Coextrudable adhesives and products therefrom
US6320116B1 (en) 1997-09-26 2001-11-20 Evergreen Solar, Inc. Methods for improving polymeric materials for use in solar cell applications
US6632518B1 (en) 1998-10-14 2003-10-14 E. I. Du Pont De Nemours And Company Fluoropolymer film structures and laminates produced therefrom
DE69924025T2 (en) 1998-12-07 2005-07-21 Bridgestone Corp. COVER MATERIAL FOR SOLAR CELL
JP3978911B2 (en) * 1998-12-07 2007-09-19 株式会社ブリヂストン Solar cell cover material, sealing film, and solar cell
JP2000294813A (en) * 1999-04-07 2000-10-20 Bridgestone Corp Back cover material for solar cells and solar cell
US6414236B1 (en) 1999-06-30 2002-07-02 Canon Kabushiki Kaisha Solar cell module
JP4797272B2 (en) 2001-04-12 2011-10-19 住友化学株式会社 Solar cell exterior body
DE10394373B4 (en) 2002-12-16 2016-06-02 Dai Nippon Printing Co., Ltd. Intermediate foil for a solar cell module and solar cell module, in which the intermediate foil is used
US20040202866A1 (en) 2003-04-11 2004-10-14 Kernander Carl P. Bright white protective laminates
JP2006066762A (en) 2004-08-30 2006-03-09 Canon Inc Flexible solar cell module and its installation method
JP2006152013A (en) * 2004-11-25 2006-06-15 Teijin Dupont Films Japan Ltd Easily adhesive polyester film for solar cell back surface-protecting film and solar cell back surface-protecting film obtained using the same
JP2006165169A (en) 2004-12-06 2006-06-22 Canon Inc Solar cell module, manufacturing method thereof and installing method thereof
JP2006165232A (en) 2004-12-07 2006-06-22 Canon Inc Solar cell module, manufacturing method thereof and installing method thereof
KR101463708B1 (en) 2005-06-13 2014-11-19 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Fluoropolymer containing laminates
US7553540B2 (en) 2005-12-30 2009-06-30 E. I. Du Pont De Nemours And Company Fluoropolymer coated films useful for photovoltaic modules
US8012542B2 (en) 2005-12-30 2011-09-06 E.I. Du Pont De Nemours And Company Fluoropolymer coating compositions containing adhesive polymers and substrate coating process
JP5125012B2 (en) 2006-07-25 2013-01-23 凸版印刷株式会社 Solar cell backside sealing sheet
US7847184B2 (en) 2006-07-28 2010-12-07 E. I. Du Pont De Nemours And Company Low modulus solar cell encapsulant sheets with enhanced stability and adhesion
JP5167622B2 (en) 2006-10-26 2013-03-21 凸版印刷株式会社 Solar cell module
US20080128018A1 (en) 2006-12-04 2008-06-05 Richard Allen Hayes Solar cells which include the use of certain poly(vinyl butyral)/film bilayer encapsulant layers with a low blocking tendency and a simplified process to produce thereof
US20080135091A1 (en) 2006-12-08 2008-06-12 Lap Kin Cheng Process and device to produce a solar panel with enhanced light capture
US8124221B2 (en) 2006-12-21 2012-02-28 E. I. Du Pont De Nemours And Company Crosslinkable vinyl fluoride copolymer coated film and process for making same
JP2008181929A (en) 2007-01-23 2008-08-07 Toppan Printing Co Ltd Solar cell rear surface protective sheet and solar cell module
WO2008112529A1 (en) * 2007-03-09 2008-09-18 3M Innovative Properties Company Multilayer film
US20090162652A1 (en) 2007-12-21 2009-06-25 Ranade Aditya P Co-extruded fluoropolymer multilayer laminates
US20090255571A1 (en) 2008-04-14 2009-10-15 Bp Corporation North America Inc. Thermal Conducting Materials for Solar Panel Components
CN102067328A (en) 2008-06-26 2011-05-18 三井-杜邦聚合化学株式会社 Laminated sheet for solar cell, and solar cell module comprising the same
CN101350370B (en) * 2008-09-18 2010-09-22 杭州福斯特光伏材料股份有限公司 Backboard material for solar cell assembly
FR2941888B1 (en) 2009-02-06 2011-03-25 Arkema France USE OF A FILM COMPOSED OF POLYOLEFIN IN A PHOTOVOLTAIC MODULE
CN102039664B (en) 2009-10-10 2013-11-27 E.I.内穆尔杜邦公司 Superposition method for multilayer film and solar battery backplane manufactured by method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010101582A1 *

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